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Kiran Singhal et al., IJSIT, 2012, 1(2), 69-84 IJSIT (www.ijsit.com), Volume 1, Issue 2, November-December 2012 69 HALO AND PSEUDOHALO-DEMETALLATION IN TETRA AND PENTA- ORGANOMETAL AND METALLOIDS KIRAN SINGHAL*, SUBHAS KUMAR CHAUDHARY, RAJESH KUMAR MALL AND PREM RAJ Department of Chemistry, Lucknow University Lucknow-226007, India ABSTRACT Halo and pseudohalo demetallation reactions of higher valent pentaphenyl arsenic and antimony and, tetrapolyfluorophenyl tin have been carried out employing halogens X2 (X = Br, I) interhalogens IX (X = Cl, Br), ICl3, pseudohalogen (SCN)2, halo-pseudohalogens XSCN (X = Cl, Br) IN3, INCO and, metallic halides TeCl 4 and (NH4)2PbCl6. Reaction of (C6H5)5M (M= As,Sb) with these electrophiles afforded corresponding arsonium and stibonium derivatives (C6H5)4MX while reactions of tetrafluorophenyl tin (C6F5)4Sn with halogens and interhalogens yielded corresponding (C6F5)nSnX4-n (X = Cl, Br n = 2,3) derivatives depending upon the molar ratio of reactants and the reaction conditions. The products have been identified by m.p. elemental analysis and spectroscopic data. Keywords: Pentaphenyl arsenic and antimony, tetrahalophenyltins, halogens, pseudohalogens, halopseudohalogens, metallic halides. Graphical abstract: Halogens, interhalogens, pseudohalogens and metallic halides cleave metal-carbon bond(s) from R5M (M = As, Sb) under varying conditions. M R 4 + IX M I + X - R 4 R 4 MX + RI + Keywords: Pentaphenyl arsenic and antimony, tetrahalophenyltins, halogens, pseudohalogens, halopseudohalogens, metallic halides.

HALO AND PSEUDOHALO-DEMETALLATION IN TETRA AND PENTAORGANOMETAL AND METALLOIDS

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Halo and pseudohalo demetallation reactions of higher valent pentaphenyl –arsenic and antimony and, tetrapolyfluorophenyl tin have been carried out employing halogens X2 (X = Br, I) interhalogens IX (X = Cl, Br), ICl3, pseudohalogen (SCN)2, halo-pseudohalogens XSCN (X = Cl, Br) IN3, INCO and, metallic halides TeCl4 and (NH4)2PbCl6. Reaction of (C6H5)5M (M= As,Sb) with these electrophiles afforded corresponding arsonium and stibonium derivatives (C6H5)4MX while reactions of tetrafluorophenyl tin (C6F5)4Sn with halogens and interhalogens yielded corresponding (C6F5)nSnX4-n (X = Cl, Br n = 2,3) derivatives depending upon the molar ratio of reactants and the reaction conditions. The products have been identified by m.p. elemental analysis and spectroscopic data

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Page 1: HALO AND PSEUDOHALO-DEMETALLATION IN TETRA AND PENTAORGANOMETAL AND METALLOIDS

Kiran Singhal et al., IJSIT, 2012, 1(2), 69-84

IJSIT (www.ijsit.com), Volume 1, Issue 2, November-December 2012

69

HALO AND PSEUDOHALO-DEMETALLATION IN TETRA AND PENTA-

ORGANOMETAL AND METALLOIDS

KIRAN SINGHAL*, SUBHAS KUMAR CHAUDHARY, RAJESH KUMAR MALL AND PREM RAJ

Department of Chemistry, Lucknow University Lucknow-226007, India

ABSTRACT

Halo and pseudohalo demetallation reactions of higher valent pentaphenyl –arsenic and antimony and,

tetrapolyfluorophenyl tin have been carried out employing halogens X2 (X = Br, I) interhalogens IX (X = Cl, Br), ICl3,

pseudohalogen (SCN)2, halo-pseudohalogens XSCN (X = Cl, Br) IN3, INCO and, metallic halides TeCl4 and (NH4)2PbCl6.

Reaction of (C6H5)5M (M= As,Sb) with these electrophiles afforded corresponding arsonium and stibonium derivatives

(C6H5)4MX while reactions of tetrafluorophenyl tin (C6F5)4Sn with halogens and interhalogens yielded corresponding

(C6F5)nSnX4-n (X = Cl, Br n = 2,3) derivatives depending upon the molar ratio of reactants and the reaction conditions.

The products have been identified by m.p. elemental analysis and spectroscopic data.

Keywords: Pentaphenyl –arsenic and –antimony, tetrahalophenyltins, halogens, pseudohalogens, halo–

pseudohalogens, metallic halides.

Graphical abstract: Halogens, interhalogens, pseudohalogens and metallic halides cleave metal-carbon bond(s)

from R5M (M = As, Sb) under varying conditions.

MR4+ IX

M I+

X-

R4

R4MX + RI+

Keywords: Pentaphenyl –arsenic and –antimony, tetrahalophenyltins, halogens, pseudohalogens, halo–

pseudohalogens, metallic halides.

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INTRODUCTION

Despite a considerable interest in the electrophilic cleavage and oxidative addition reactions of symmetrical

tetra and hexa-organometallics of group 14 and symmetrical trivalent group 15 organometallic derivatives involving

metal-carbon and metal-metal bonds based on hydrocarbon ligands with halogens X2 (X= Cl, Br, I), interhalogens IX

(X= Cl, Br), ICl3, pseudohalogens (SCN)2, halo-pseudohalogens (IN3, INCO,) metallic halides (HgCl2, TeCl4, SbCl5),

positive halogen containing heterocyclic derivatives viz. N-bromosuccinimide, N-halophthalimide and N-

chlorobenzotriazole, reactions of pentaphenylarsenic, -antimony and -bismuth (R5M, M= As, Sb,) and

tetra(pentafluorophenyl)tin and -lead have been reported to a limited extent.[1-11] Apart from this, reactions of less

common electrophiles viz, ClSCN, BrSCN, (NH4)2PbCl6, with pentaaryl arsenic, -antimony and -bismuth are yet to be

investigated. Sowerby etal[10] have partially examined the oxidative addition reactions of R3Sb (R= Ph, Me) with BrSCN

and ClSCN. Reactions of diammonium hexachloro plumbate (NH4)2PbCl4 and diselenocyanogen (SeCN)2 have been

reported to limited extent.[1] However, oxidative addition reactions of such electrophiles with tris(pentafluorophenyl)

antimony have been investigated by Singhal etal. [4-7] Reactions of pentaphenyl arsenic, -antimony and –bismuth in

higher valent with these electrophiles have not been reported so for. The lack of published data coupled with our

interest on the oxidative addition and electrophilic cleavage reactions of group 14 and 15 metal-carbon bond(s) we

now wish to report.

Reactions of Ph5M (M= As, Sb,) with halogens (Cl, Br, I) interhalogens ICl, IBr and ICl3, and less common

electrophiles such as IN3, INCO, (SCN)2, ClSCN, BrSCN, and metallic halides (NH4)2PbCl6, TeCl4 and HgCl2

which have not been reported to date.

Reactions of tetra (pentafluorophenyl)tin with halogens and interhalogens.

Apart from synthetic utility to provide newer organometallic derivatives which are otherwise difficult to obtain,

these reactions provide an insight to the relative case of cleavage of an organic group from the metal. Reactions of less

common electrophiles INCO, IN3 have earlier been used for regio and stereo specific addition in synthetic organic

chemistry.

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EXPERIMENTAL

Pentaaryl –arsenic and –antimony and tetra is (polyfluorophenyl) tin were prepared by the reported methods [1-3]

ICl, ICl3, TeCl4 (Sigma Aldrich) were used without further purification. (NH4)2PbCl, (NH4)2PbCl6 was prepared by the

reported procedure. (SCN)2, IN3, INCO, XSCN(X = Cl, Br) were freshly generated in solution before use. A few

experiments are given below. Further details are given in Tables-1 to 4.

Reactants Molar ratio Products Melting point oC Temp. & solvent

Ph5Sb+ (NH4)2PbCl6 1:1 Ph4SbCl

205oC

Room temp.

CCl4

Ph5Sb + TeCl4 1:1 Ph4SbCl

PhTeCl3

205oC Room temp.

Toluene

Ph5Sb + TeCl4 1:1 Ph3SbCl2

Ph2TeCl2

142oC

Reflux temp.

Toluene

Ph5As+ (NH4)2PbCl6 1:1 Ph4AsCl

256oC

Room temp.

CCl4

Ph5As + TeCl4 1:1 Ph4AsCl

PhTeCl3

256oC Room temp.

Toluene

Ph5As + TeCl4 1:1 Ph3AsCl2

Ph2TeCl4

205oC Reflux temp.

Toluene

Table 1: Reaction with metallic halides

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Reactants Molar ratio Products Melting point (0oC) Temp. & solvent

Ph5Sb + 2ICl

1:2 Ph3SbCl2 142 0oC

Acetonitrile

Ph5As + 2ICl

1:2 Ph3AsCl2 205 0oC

Acetonitrile

Ph5Sb + ICl3

1:1 Ph3SbCl2 142 0oC

Acetonitrile

Ph5As + Br2

1:1 Ph3AsBr2 213 -5oC

CCl4

Ph5Sb + (SCN)2

1:1 Ph4Sb(SCN)

PhSCN

226 -5oC

CCl4

Ph5As + (SCN)2

1:1 Ph4As(SCN)

PhSCN

130 -5oC

CCl4

Ph5Sb + BrSCN

1:1 Ph4SbBr

PhSCN

210 0oC

Acetonitrile

Ph5Sb + ClSCN

1:1 Ph4SbCl

PhSCN

205 0oC

Acetonitrile

PH5As + BrSCN

1:1 Ph4AsBr

PhSCN

314 0oC

Acetonitrile

Ph5Sb + IN3 1:1 Ph4SbN3

PhI

190 -10oC

Acetonitrile

Ph5Sb + INCO

1:1 Ph4SbNCO

PhI

140 0oC

Acetonitrile

Ph5As + I2

1:1 Ph4AsI

PhI

315 Room Temp.

Methyl Cyanide

Ph5Sb + I2

1:1 Ph4SbI

PhI

200 Room Temp.

Methyl Cyanide

Ph5As + 2IBr

1:2 Ph3AsBr2

PhI

213 Room Temp.

CCl4

Ph5Sb + 2IBr

1:2 Ph3SbBr2

PhI

214 Room Temp.

CCl4

Table 2: Reaction with Halogens, interhalogensand pseudohalogens

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Compound Molecular

formula

M.P. (Lit) oC Yield (%) Ref.

Ph4Sb(SCN) C25H20NSSb 226

(226-228)

70 14

Ph4As(SCN) C25H20AsNS

130

(131)

60 13

Ph4SbN3 C24H20N3Sb

190

(191)

65 14

Ph4SbNCO C25H20NOSb

140

(141)

67 14

Ph4SbBr C24H20BrSb

210

(210-212)

63 14

Ph4SbCl C24H20ClSb

205

(204-205)

58 14

Ph4AsCl C24H20AsCl

256

(257)

72 15

Ph4AsBr C24H20AsBr 314

(319)

57 15

Ph4AsI C24H20AsI 315

(314-319)

62 12,13

Ph3SbCl2 C18H15SbCl2 142

(143.5)

56 13

Ph3AsCl2 C18H15AsCl2 205

(205)

70 12

Ph4SbI C24H20SbI

200

(200)

67 14

Ph3SbBr2 C18H15SbBr2 214

(216)

72 15

Ph4As(SCN) C25H20AsNS

130

(131)

60 13

Ph3AsBr2 C18H15AsBr2 213

(213-214)

56 15

Table 3: Analytical data of tri and tetraaryl antimony (V) derivatives

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Compound

Empirical

Formula

Molecular

Weight Found (Calcd.)

% - C

Found (Calcd.)

% - H

Found (Calcd.)

% - N

Ph4Sb(SCN)

C25H20NSSb 488.26 61.50

(61.22)

4.13

(4.56)

2.87

(2.98)

Ph4As(SCN) C25H20AsNS

441.42 68.02

(68.23)

4.57

(4.14)

3.17

(3.19)

Ph4SbN3 C24H20N3Sb

472.22 61.05

(61.12)

4.27

(4.78)

8.90

(8.81)

Ph4SbNCS

C25H20NSSb

488.26 61.50

(62.34)

4.13

(4.34)

2.87

(2.03)

Ph4SbNCO C25H20NOSb

472.19 63.23

(64.12)

4.56

(4.01)

2.88

(2.07)

Ph4SbBr C24H20BrSb

510.08 56.51

(56.12)

3.95

(3.45)

-

Ph4SbCl C24H20ClSb

465.63 61.91

(61.12)

4.33

(4.10)

-

Ph4AsCl C24H20AsCl

418.79 68.83

(68.34)

4.81

(4.48)

-

Ph4AsBr C24H20AsBr 463.24 62.23

(62.14)

4.35

(4.01)

-

Ph4AsI C24H20AsI 510.24 56.49

(56.34)

3.95

(3.67)

-

Ph3SbCl2 C18H15SbCl2 423.98 50.99

(50.45)

3.57

(3.41)

-

Ph3AsCl2 C18H15AsCl2 377.14 57.32

(57.56)

4.01

(4.90)

-

Ph4SbI C24H20SbI

557.08 51.74

(51.39)

3.62

(3.09)

-

Table 4: Elemental Analysis of Metal and Organometal -Halides/-pseudohalides

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Reaction of Pentaphenylarsenic with ICl (1:2):

Iodine monochloride (3.4g, 0.02 mol) in acetonitrile was slowly added to a well stirred and chilled cold (0oC)

suspension of pentaphenylarsenic (4.6g, 0.01 mol) in the same solvent. The initial blood-red colour of ICl solution

disappeared immediately after each addition. The mixture was further stirred for 30 min to ensure complete reaction

and then worked up. The residue (after distilling off PhI) was recrystallised from pet. Ether and identified as

triphenylarsinic dichloride.

M.P.:- 205°C Lit.:- 205°C [12]

Reaction of Pentaphenylantimony with ICl (1:2):

Ph3SbCl2 was prepared same by method as described above from Iodine monochloride (3.4g 0.02 mol) and

pentaphenylantimony (5.02g 0.0099mol) in acetonitrile.

M.P.:- 142°C Lit.: 143.5°C [13]

Reaction of Pentaphenylantimony with ICl3:

Iodine trichloride (2.33g 0.01mol) in acetonitrile was slowly added to a well stirred and chilled cold (0oC)

suspension of pentaphenylantimony (5.07g 0.01mol) in same solvent. The mixture was further stirred for 30 min. to

ensure complete reaction and worked up. The residue (after distilling PhI) was recrystallised from pet. Ether and

identified as triphenylantimony dichloride.

M.P.:- 142°C Lit. : 143.5°C [13]

Reaction of Pentaphenylantimony with I2 (1:1):

A solution of I2 (2.53g, 0.01 mol) in methyl cyanide was added dropwise for 30 min to a well stirred solution

of pentaphenylantimony (5.07g 0.01 mol) in CH3CN at room temperature. The violet colour of I2 disappeared after

each addition. Towards the end of the reaction the solution changed its colour to pink. Subsequently, the solution was

stirred for 1h. It was freed from solvent and phenyl iodide distilled off. The residue was recrystallised from pet. Ether

to give Ph4SbI.

M.P.:- 200°C Lit.: 200°C [14]

Reaction of Pentaphenylarsenic with Bromine (1:2):

A solution of bromine (3.2g 0.02 mol) in CCl4 was added dropwise over a period of half an hour to a well

stirred cold (-5oC) suspension of pentaphenylarsenic (4.6g 0.01 mol) in CCl4. The initial red colour of bromine

immediately disappeared after each addition. At the end of the reaction the solution was further stirred for half an

hour. It was then free from the solvent and the residue was distilled at reduced pressure to give triphenylarsenic

dibromide.

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M.P.:-213°C Lit.:- 213-214°C [15]

Reaction of Pentaphenylantimony with (SCN)2:

A freshly prepared solution of thiocyanogen in CCl4 (30ml) was added with stirring to pentaphenylantimony

(5.07g 0.01mol) in CCl4 (50ml) subsequently stirred for 1h and warmed to room temperature. The removal of the

solvent under reduced pressure afforded a crystalline solid. After recrystallization from ethanol it was characterised

as tetraphenylantimony thiocyanate.

M.P.:- 226°C Lit.:- 226-228°C [14]

Similarly reaction of pentaphenylarsenic and thiocyanogen yielded tetraphenylarsenic thiocyanate.

M.P.:- 130°C Lit.:- 131°C [13]

Reaction of Pentaphenylantimony with IN3:

A freshly generated solution of Iodine azide (1.68g 0.01mol) in acetonitrile (50ml) at -10oC was added to

stirring solution of pentaphenylantimony (5.07g 0.01mol) in the same solvent (50ml) during 15min under nitrogen

atmosphere. The reactant were stirred for 1h at initial temp. and then allowed to come at room temp. The solution

was evaporated under reduced pressure and cooled overnight, after adding pet. ether crystalline solid was obtained

characterised as tetraphenyhlantimony azide.

M.P.:- 190°C Lit.: 191°C [14]

Reaction of Pentaphenylantimony with BrSCN:

In a typical experiment a freshly generated red brown colour solution of BrSCN was added dropwise to Ph5Sb

(5.07g 0.01mol) over a period of 30min. at 0oC temp. and contents were stirred for 2h more. After usual work-up

tetraphenylantimony bromide was obtained.

M.P.:- 210°C Lit.: 210-212°C [14]

Similarly, the reaction of thiocyanate bromide and Ph5As yielded Ph4AsBr

M.P.:- 314°C Lit.: 319°C [15]

Reaction of Pentaphenylantimony with ClSCN:

Freshly generated golden yellow solution of ClSCN was added to Ph5Sb (5.07g 0.01mol) in 100ml CCl4 over a

period of 30 min. in ice cold temp. The reactants were stirred at the same temp. After work-up in usual fashion,

tetraphenylantimony chloride was obtained.

M.P. :- 205°C Lit.:204-205°C [14]

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Reaction of Pentaphenylantimony with (NH4)2PbCl6 (1:1):

Pentaphenylantimony (5.07g 0.01mol) and ammonium hexachloroplumbate (4.56g 0.01mol) were stirred in

pet. ether for 1h at room temperature. The initial bright-yellow colour of (NH4)2PbCl6 changed to creamish white.

After the completion of the reaction, the inorganic halides was filtered and washed twice with acetonitrile.

Evaporation of the solvent yielded tetraphenylantimony chloride.

M.P.:- 205°C Lit.:- 204-205°C [14]

Similarly the reaction of pentaphenylarsenic and ammonium hexachloroplumbate at room temp. yielded

Ph4AsCl

M.P.:- 256°C Lit.:- 257°C [15]

Reaction of Pentaphenylantimony with TeCl4 (1:1 Room Temperature):

A mixture of pentaphenylantimony (5.07g 0.01mol) and TeCl4 (2.69g 0.01mol) in toluene were stirred at room

temperature for 1h and filtered. The filterate on concentration yielded tetraphenylantimony chloride.

Phenyltellurium trichloride being insoluble was separated as off white solid.

Ph4SbCl M.P.:- 205°C Lit.:- 204-205°C [15]

PhTeCl3 M.P.:-214°C Lit.:- 214-216°C [15]

Reaction of Pentaphenylantimony with TeCl4 (Reflux Temperature):

Pentaphenyl antimony (5.07g 0.01mol) in 100ml toluene and TeCl4 (2.69g 0.01mol) in the same solvent (40ml) were

refluxed together for 3hrs. diphenyltellurium dichloride obtained as insoluble off white solid was filtered out.

M.P.:- 158°C Lit. :-160°C [15]

The filtrate on concentration yielded Ph3SbCl2

M.P.:-142°C Lit. :-143.5°C [13]

Reactions of (C6F5)4Sn with ICl:

A solution of iodine monochloride 3.24g(0.02mol) in carbon tetrachloride was added dropwise to a solution of

tetrakis(pentafluorophenyl)tin 7.86g(0.01mol) in the same solvent over a period of 30 minutes. After each addition

colour of ICl faded away. The reaction mixture was stirred for a period of one hrs to ensure completion of the reaction.

The solvent was distilled off at reduced pressure to leave behind a viscous mass which could not be crystallised. It was

isolated as DMSO complex and characterized as (C6F5)2SnCl2.2DMSO.

M.P.:- 129°C Lit.:- 130°C [16]

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RESULTS AND DISCUSSION

In earlier communications reported from our laboratory cleavage of metal-carbon bond from

tetraorganometallics both symmetrical and unsymmetrical (M= Si, Ge, Sn, Pb) employing halogens, interhalogens and

pseudohalogens has been reported.[2-10] Similarly, the oxidative addition reactions of triaryl-arsenic and –antimony

with such electrophiles has been substantially reported. Contrasting behaviour of triarylbismuth compounds where

cleavage of bismuth-carbon bond rather than addition to bismuth oxidatively has been observed. In view of the

limited data available for the cleavage reactions of pentaphenyl-arsenic and -antimony with less common

electrophiles we undertook a systematic study on higher valent arsenic and antimony compounds reported herein

together with other systems.

Cleavage Reactions of Pentaphenyl-Arsenic and –Antimony:

Both ICl and ICl3 are strong electrophiles and cleave two M-C bonds from Ph5M (M= As, Sb) irrespective of the

molar ratio of the electrophile used.

Ph5Sb + 2ICl Ph3SbCl2 + 2PhI ...(1)

Ph5As + 2ICl Ph3AsCl2 + 2PhI ...(2)

Ph5Sb + ICl3 Ph3SbCl2 + 2PhI + Cl2 ...(3)

Ph5As + ICl3 Ph3AsCl2 + 2PhI + Cl2 ...(4)

Even with an excess of ICl futher cleavage of As-C or Sb-C bond was not observed. It is surprising since

bromine which is an equally strong electrophile like ICl has been reported to produce Ph3AsBr4 in the sense of

equations shown below (Eqs.5 & 6)

Ph5As + Br2 Ph3AsBr2 ...(5)

Ph3AsBr2 + Br2 Ph3AsBr4 ...(6)

Bromination of pentaphenylantimony produced triphenylantimony dibromide at 0oC irrespective of the

molar ratio of bromine used. However, iodine cleavage of Ph5Sb yielded tetraphenylantimony iodide with 1 mole of I2

and triphenylantimony diiodide with 2 moles of I2, respectively. Addition of three moles of bromine and iodine was

not successful in producing triphenylantimony tetrahalides presumably due to the reduced nucleophilic character of

antimony-phenyl bonds in triphenylantimony dihalides as compared to that in pentaphenylantimony. Reactions of

iodine monochloride with pentaphenylantimony invariably produced Ph3SbCl2 at a lower temperature, irrespective of

the molar ratio of the electrophiles used. However, 1:1 and 1:2 molar reactions of IBr with Ph5Sb gave Ph4SbBr and

Ph3SbBr2 at room temperature and 70o respectively.

The extent of cleavage is confined only to the removal of two phenyl groups from pentaphenylarsenic or –

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antimony compounds with iodine monochloride and iodine trichloride which was confirmed by treating the

pentaphenylarsenic or –antimony compounds with an excess amount (>2mole) of the iodine halides. Formation of

diphenyl-metal (V) trihalides did not take place on prolong stirring. This observation is also supported by the fact that

iodine monochloride did not decolourise in refluxing CH3CN when treated against Ph3MCl2 and unreacted starting

material was recovered quantitatively. An argument in favour of cleavage of two phenyl groups from

pentaphenylarsenic is also based on the observation that a similar reagent Br2 reacts with Ph3AsBr2 to produce

Ph3AsBr4. No further cleavage was observed. Reaction of IBr and I2 with pentaaryl-arsenic and –antimony proceeded

in the sense shown below.

Ph5Sb + IBr Ph4SbBr + PhI ...(7)

Ph5Sb + I2 Ph4SbI + PhI ...(8)

The observation made with IBr and I2 are in line with the fact that the Sb-C bond in more reactive than As-C.

Also the fission of second As-C in these reactions proceeds less readily due to reduced nucleophilic character of As-C

bond coupled with the less polar nature of IBr and I2. However, there seems to be no kinetic study so far which have

been carried out on this second fission reactions in pentaphenylarsenic.

From the results reported above and from our earlier investigations, the reactivity was found to be in the

orders, Br2 ≈ ICl > IBr > I2 and As-C < Sb-C > Bi-C which is also the decreasing order of their bond polarity.

The formation of Ph3AsCl4 was not observed with either of the electrophile. Both I2 and IBr are weak

electrophils and have been reported to cleave one metal-carbon bond both from Ph4E (E= Sn, Pb) and Ph5M (M= As,

Sb).[17] Pseudohalogen like (SCN)2 and pseudohalogens BrSCN and ClSCN are still weaker electrophiles but were

found to cleave one As-C and Sb-C bond from Ph5M at 0o in acetonitrile.

Ph5Sb + (SCN)2 Ph4Sb(SCN) + PhSCN ...(9)

Ph5As + (SCN)2 Ph4As(SCN) + PhSCN ...(10)

Ph5Sb + BrSCN Ph4SbBr + PhSCN ...(11)

Ph5Sb + ClSCN Ph4SbCl + PhSCN ...(12)

Ph5As + BrSCN Ph4AsBr + PhSCN ...(13)

Even with an excess of freshly generated solution of (SCN)2, BrSCN and ClSCN no further cleavage was

observed. On raising the temperature above 0°C polymerisation of (SCN)2 and XSCN (X= Cl, Br) preceded the cleavage.

The study also provide an insight into the relative reactivity of X2 (X= Cl, Br) with respect to (SCN)2. Both Cl2 and Br2

being more electronegative get attached to arsenic and antimony. It may be noted that both BrSCN and ClSCN are

oxidatively added to Ph3M (M= As, Sb) to give oxidative addition products Ph3MXSCN (X= Cl, Br) and cleave metal-

carbon bond from Ph4E (E= Sn, Pb) to a limited extent[5-8]. Further cleavage from Ph5E is possible to give dithiocyanate

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or dihalide products and even more halogenated products in presence of AlCl3 as catalyst as has been reported for

group 14 organometallics.[1] However, such reactions were not attempted as the organometallic products formed after

the reactions are not expected to survive the drastic condition of hydrolysis.

IN3 and INCO, which are still weaker electrophiles and were found to cleave one As-C bond from Ph5As and

one Sb-C bond from Ph5Sb but to a limited extent and the yield of the product is low. This suggests that (i) both IN3

and INCO are also weaker electrophile as compared to XSCN (X= Cl, Br) and (SCN)2 and (ii) Sb-C bond is much more

reactive as compared to As-C bond as indicated by the yield of the products. We have earlier reported that IN3 and

INCO cleaved metal-carbon (Sn) bond only in presence of AlCl3 while the reaction of tetraorganolead with (SCN)2,

BrSCN and ClSCN proceed at 0°C in absence of AlCl3.[2-8]

Ph5Sb + IN3 Ph4SbN3 + PhI ...(14)

Ph5As + IN3 Ph4AsN3 + PhI ...(15)

Ph5Sb + INCO Ph4SbNCO + PhI ...(16)

Ph5As + INCO Ph4AsNCO + PhI ...(17)

Reactions of Ph5Sb and ph5As were also carried out with diammonium hexachoroplumbate which has been

used in past as chlorinating agent especially, in the cleavage reactions of tetraaryl leads. While the cleavage of Pb-C

bond in tetraaryleads employing chlorine is uncontrolled and more than three lead-carbon bonds are cleaved.

Reactions with (NH4)2PbCl6 is limited to the cleavage of two lead-carbon bonds due to the slow release of chlorine. In

the present investigation reaction of pentaphenyl antimony and pentaphenylarsenic proceeded with the cleavage of

only one Sb-C and As-C bond respectively.

Reaction of Ammonium Hexachloroplumbate (NH4)2PbCl6 with Ph5M (M= As, Sb):

(NH4)2PbCl6 is a slow chlorinating agent which dissociate in the sense of equation show below

(NH4)2PbCl6 2NH4Cl + PbCl2 + Cl2 …(25)

The slow release of Cl2 in solution such as acetonitrile has been used in the past for the controlled cleavage of

tetraarylleads to give diaryllead dihalides. Direct chlorination of tetraaryllead is quite devastating and cleave two Pb-C

bonds to give ultimate product PbCl2. However with the slow release of Cl2 in solution exclude the cleavage beyond

more than two lead-carbon bonds

In case of Ph5M, cleavage of both As-C and Sb-C bond was observed. It is interesting to note in both the case

only cleavage of one metal-carbon bond was observed.

Ph5M + (NH4)2PbCl6 Ph4MCl + 2NH4Cl + PbCl2+ PhC … (26)

Both Ph4SbCl and Ph4AsCl were separated from the mixture being soluble in organic solvents while NH4Cl and

PbCl2 being insoluble in the solvent are easily separated out.

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Ph5M + (NH4)2PbCl6

CCl4r.t. Ph4MCl + 2NH4Cl + PbCl2 + PhCl … (18)

(M= As, Sb)

Tetraphenylstibonium and –arsenium being soluble in organic solvent are easily separated out from the

solution.

Similarly, the reaction of tellurium tetrachloride at room temperature proceeded with the cleavage of one Sb-

C from pentaphenylantimony.

Ph5Sb + TeCl4 Ph4SbCl + PhTeCl3 …(19)

However, at reflux temperature of toluene two Sb-C carbon bonds are cleaved.

Ph5Sb + TeCl4 Ph3SbCl2 + Ph2TeCl2 …(20)

Similar course of reaction was observed with Ph5As

Ph5As + TeCl4

r.t.toluene Ph4AsCl + PhTeCl3 …(21)

Ph5As + TeCl4

toluenereflex temperaturePh3AsCl2 + Ph2TeCl2 …(22)

The mechanism of such reactions may possibly involve a four centered transition state in which nucleophilic

attack on metal atom (facilitated by the availability of vacant d-orbitals) by incipient chloride or bromide ion is

synchronous with electrophilic attack by incipient iodide ion on carbon atom of the aromatic rings. Similar

mechanism has earlier been suggested for the cleavage of group 14 compounds with halogens and interhalogens.[1-11,

16]

Cleavage Reactions with Tetrakis(pentafluorophenyl)tin:

Both ICl and Br2 are strong electrophile and have been reported to cleave two tin-aryl bonds from

symmetrical and unsymmetrical tetraaryltins. Reaction of tetrakis(polyfluorophenyl)tin were expected to proceed in

the same fashion but the extent of cleavage has not been studied so far. In the present study the author has found

cleavage reaction to proceed in the sense of equation shown below.

(C6F5)4Sn + 2IClCCl4 (C6F5)2SnCl2 + 2C6F5I …(23)

Similarly bromine which is equally strong electrophile cleave to yielded bis(pentafluorophenyl)tin dibromide.

(C6F5)4Sn + 2Br CCl4 (C6F5)2SnBr2 + 2C6F5Br …(24)

Both ICl and Br2 are strong electrophile and cleave two Sn-C6F5 bond to yield corresponding dihalides which

is parallel to the reactions observed with tetraphenhyltin. However (C6F5)2SnCl2 are obtained as a viscous mass and

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the attempts to recrystallize it could not be successful. Alternatively it was characterized as its DMSO complex

(C6F5)2SnCl2.2DMSO which is white solid having satisfactory elemental analysis and IR.

Thus the cleavage pattern of partially or fully substituted phenyl group is same as for tetraphenyltin. In all the

case at least two Sn-C bond are cleaved and that too at room temperature.

Infrared spectra:

The title compounds were also identified on the basis of their infrared spectra in the range (4000cm-1–

200cm-1). Absorption frequencies associated with phenyl groups bound to the metal atom, do not show any significant

change. The thiocyanato group is capable of bonding through N or S of NCS group. Absorptions associated with

various modes of vibrations of the pseudohalide group have been identified and indicate the nature of bonding to the

antimony atom. The chalcogen group NCS gives rise to three fundamental modes of vibration due to υ(C N), υ(C-S)

and δ(NCS). The υasy NCS mode appears as a broad band of strong intensity at 2060 cm-1 and is fully consistent with a

N-bonded NCS group, in consonance with the usual isostructure reported for tetraphenylantimony isothiocyanates[18-

22]

Further it has been reported that the intensity of υasy NCS mode is 50-100 times stronger than that of υasy SCN

and the shape is broad for the former and sharp in the latter case. The position intensity and the shape of υNCS thus

suggest an isostructure.[22]

The δ NCS mode which is virtually υC-S mode, according to established views, lies at distinctly higher

frequency in the isothiocyanates (760-880cm-1) and is a deciding factor about the nature of pseudohalide in these

compounds. Thus, the appearance of a medium intensity band at 860 cm-1 in all the derivatives suggests an

isostructure. Further, the appearance of a band at 472±2 is suggestive of the presence of M-N bonding.

As for mass sensitive frequencies a medium strong band appearing in the region 450-488cm-1 can be assigned

to Sb stretching frequencies corresponding to y mode. Absorption frequencies corresponding to the t mode appear in

the region 240-220 cm-1. The values are good agreement with the reported frequencies of the Sb-C bond in Ar4SbX

derivatives (X= halo or pseudohalo group).[18,19]

CONCLUSION

The noteworthy features of cleavage reactions reported herein are

Br2, ICl and ICl3 act as strong electrophiles towards M-C bond(s) (M= As, Sb)

Not more than two metal-carbon bond(s) are cleaved employing Br2 and further addition of Br2 leads to the

formation of heptavalent compounds particularly in case of arsenic viz., Ph3AsBr4.

Pseudohalogen (SCN)2, interhalopseudohalogens IN3, INCO and XSCN (X= Cl, Br) are capable of cleaving only

one metal-carbon bond from Ph5M but the reactions are sluggish. On the basis of yield the reactivity of these

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electrophiles can be arranged in the order ClSCN > BrSCN > (SCN)2 > IN3 > INCO.

On the basis of nature of products the polarity of XSCN appear to be Clδ--SCNδ+ and Brδ--SCNδ+. Thus Cl and Br

are more electro negative than (SCN).

Diammonium hexachloroplumbate (NH4)2PbCl6 can be used as chlorinating agent. Due to slow release of

chlorine, the formation of heptavalent compound does not take place.

Reactions with TeCl4 in varying conditions provide PhTeCl3 and Ph2TeCl2 derivatives in high yield and high

purity together with onium salts Ph4MCl (M= As, Sb) which otherwise involve tedious quarterization reaction

involving triarylmetals Ar3M and arylhalides in presens of Lewis acid catalylst at higher temperature.

The reactivity of M-C bond (M= As, Sb, Bi) can be arranged in the order As-C > Sb-C > Bi-C.

Both IBr and I2 are weak electrophiles as compared to ICl and Br2.

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